KR20160021757A - Nucleating composition and thermoplastic polymer composition comprising such nucleating composition - Google Patents

Abstract

(A) a first nucleating agent containing a cyclic dicarboxylate salt compound; And (b) a second nucleating agent containing talc, wherein the cyclic dicarboxylate salt compound is represented by formula (I): < EMI ID =
(I)

Description

NUCLEATING COMPOSITION AND THERMOPLASTIC POLYMER COMPOSITION COMPRISING SUCH NUCLEATING COMPOSITION [0001] This invention relates to a thermoplastic polymer composition,

The present invention relates to a nucleating composition comprising a salt of a metal or an organic cation of a cyclic dicarboxylic acid as a nucleating agent. The present invention also relates to a thermoplastic polymer composition containing the nucleating composition. The present invention also relates to a molded article containing the thermoplastic polymer composition.

Such nucleation compositions are known from document EP 1379368 B1. This document discloses one or more metal salts of hexahydrophthalic acid (HHPA), such as calcium, strontium, lithium and monobasic aluminum salts, which are used as nucleating agents to produce thermoplastic compositions exhibiting an improved crystallization reaction.

Various other documents also describe metal salts that are used as nucleating additives for thermoplastics. For example, US 2004/0220311 A1 discloses the use of certain hexahydrophthalic acid metal salts, such as calcium, strontium, lithium or monobasic aluminum, which are used as nucleating agents in various thermoplastics, especially polypropylene compositions. WO 2006/071721 discloses polyolefins; Dicarboxylate salt compounds such as nucleating agents containing bicyclic [2.2.1] heptanedicarboxylate salts (available under the trade name Hyperform ^® HPN-68 from Milliken &Company); A first fatty acid salt having a first cationic counterion selected from the group consisting of calcium, sodium, lithium and barium, such as calcium stearate; And a second fatty acid salt having a second cationic counterion selected from the group consisting of magnesium, aluminum and zinc, such as zinc stearate.

Nucleating agents are chemical compounds or compositions that enable faster nucleation or higher crystallization temperatures of the thermoplastic polymer, resulting in increased productivity during processing of the thermoplastic polymer and improved mechanical properties and physical properties of articles made from such thermoplastic polymers. This compound provides a nucleation site for crystal growth during cooling of the thermoplastic molten composition. In polypropylene, for example, a higher degree of crystallinity and a more uniform crystal structure are obtained by adding a talc and a nucleating agent such as a carboxylate salt, such as sodium benzoate. An overview of nucleating agents used in polypropylene-based compositions can be found, for example, in Polym. Adv. Technol. 2007, 18, 685-695. However, the use of nucleating agents is generally recognized as a very unpredictable technology field. Small changes in the molecular structure of the nucleating agent can dramatically change the ability of the nucleating agent to effectively nucleate the polymer composition. The effect of the nucleating agent on the polymer morphology during (re) crystallization of thermoplastics is not yet known.

Nucleating compositions are known from document EP 1379368 B1. This document discloses one or more metal salts of hexahydrophthalic acid (HHPA), such as calcium, strontium, lithium and monobasic aluminum salts, which are used as nucleating agents to produce thermoplastic compositions exhibiting an improved crystallization reaction.

Various other documents also describe metal salts that are used as nucleating additives for thermoplastics. For example, US 2004/0220311 A1 discloses the use of certain hexahydrophthalic acid metal salts, such as calcium, strontium, lithium or monobasic aluminum, which are used as nucleating agents in various thermoplastics, especially polypropylene compositions. WO 2006/071721 discloses polyolefins; Dicarboxylate salt compounds such as nucleating agents containing bicyclic [2.2.1] heptane dicarboxylate salts (available under the trade name Hyperform ^® HPN-68 from Milliken &Company); A first fatty acid salt having a first cationic counterion selected from the group consisting of calcium, sodium, lithium and barium, such as calcium stearate; And a second fatty acid salt having a second cationic counterion selected from the group consisting of magnesium, aluminum and zinc, such as zinc stearate.

Therefore, there is a demand for improvement in the mechanical properties of the thermoplastic composition, such as flexural modulus and impact strength.

It is an object of the present invention to provide a nucleating composition which greatly improves the mechanical properties of thermoplastic compositions such as flexural modulus and impact strength.

This purpose

(a) a first nucleating agent containing a cyclic dicarboxylate salt compound; And

(b) a nucleating agent containing a talc, wherein the cyclic dicarboxylate salt compound is represented by the formula (I):

(I)

Surprisingly, the nucleating composition of the present invention greatly improves mechanical properties such as stiffness and impact strength.

In addition, document US 2007/0213439 A1 discloses a nucleating composition containing a mixture of two nucleating agents and containing a dicarboxylate calcium salt, the first nucleating agent known as Hyperform ^® HPN-20E, in which the second nucleating agent bicyclic [2.2.1] heptane dicarboxylate contain salts, particularly Hyperform HPN-68L ^®. In addition, US 2008/0171834 Al discloses a calcium carboxylate dicarboxylate as the first nucleating agent, but uses a bis-phenol phosphate compound as the second nucleating agent in the nucleating composition. Accordingly, these documents do not disclose or suggest the application of talc as a nucleating agent with a dicarboxylate calcium salt.

Another advantage of the nucleating composition according to the present invention is that it reduces the bending of molded articles made from the nucleated thermoplastic polymer composition; Higher heat distortion temperature (HDT) and improved top load.

Another advantage of the nucleating composition according to the present invention is that it comprises a low shrinkage due to temperature changes of the shaped article made from the nucleated thermoplastic polymer composition, as measured by the linear thermal expansion coefficient (CLTE) measured according to ASTM D696. CLTE measures the change in length per unit length of a substance per unit of change in temperature. The CLTE, expressed in in / in / 또는 or cm / cm / 캜, is used to calculate dimensional changes resulting from thermal expansion. CLTE is particularly important, especially when the components of the assembly have a very different coefficient of thermal expansion. The thermal expansion of a material is another important design factor, and is an important factor in the application, especially where plastic parts composed of polymer components meet metal parts or parts that have metal inserts. In addition, the shrinkage ratio may be measured according to ISO 294-4 (shrinkage rate 3-D).

The advantage of the nucleating composition according to the invention is that it comprises one of the following preferred properties: bending elastic modulus, impact strength, CLTE and shrinkage.

The first nucleating agent in the composition according to the invention contains the calcium cis-hexahydrophthalate compound of formula (I).

^® Hyperform HPN-20E ™ nucleating agent available from Milliken calcium sheath of such formula (I) - contains compounds, such as containing a zinc stearate-stearate as hexahydro phthalate compound and an acid scavenger (scavenger).

The nucleating composition according to the present invention contains talc as a second nucleating agent.

Talc is a common additive in the industry and is mostly used as a reinforcing or filler and also as a nucleating agent for various polymer compositions. Talc is generally considered to be a filler when used in relatively large amounts, e.g., from about 10 to 50 wt%, based on the total polymer composition. When talc is used below 5 wt%, it is no longer considered as a filler and acts as a nucleating agent.

The talc has a particle size distribution defined by the present invention in powder form, preferably d ₅₀ , of from 0.1 to 20 탆, more preferably from 0.5 to 15 탆; Or 0.7 to 8 [mu] m in powder form.

The first nucleating agent and the second nucleating agent may be added to the nucleating composition according to the present invention in a very wide variety of amounts, for example, a weight ratio of 1: 1200 to 2: 1; Preferably 1: 500 to 1: 1; More preferably from 1: 100 to 1: 2; Particularly preferably in a ratio of 1: 50 to 1: 5. The advantage of adding these components in the above weight ratio range lies in the possibility of controlling the dimensional stability and mechanical properties at a high circulation time.

The nucleation composition may be used as a powder, a dry mix or a liquid blend. It can also be blended with other additives to make an additive pre-blend, or it can be blended with a low concentration of binder material, such as a wax or thermoplastic polymer that is compatible with the polymer intended to act as the nucleating agent. The nucleating composition may also be blended with the thermoplastic polymer as a master batch or concentrate. The blend may optionally contain acid scavengers and other additives such as stabilizers; May be provided with primary and secondary antioxidants. Suitable acid scavengers may include zinc stearate, calcium stearate or other stearate compounds, and hydrotalcites.

The present invention also relates to a thermoplastic polymer composition containing a thermoplastic polymer and a nucleating composition according to the present invention. As used herein, the term "thermoplastic " means a polymeric material that is melted upon exposure to a sufficiently high temperature, but re-solidified (crystallized) upon cooling. "Thermoplastic material" means a polymer that exhibits a (semi) crystalline form, especially when cooled. Suitable examples of thermoplastic polymers include polyamides such as polyamide-6, polyamide-6,6 or polyamide-4,6; Polyolefins such as polypropylene, polyethylene, polybutylene; Polyesters such as polyethylene terephthalate, polybutylene terephthalate; Polyphenylene sulfide; Polyurethane; As well as any of the polymer blends and compounds and any combinations thereof. Preferably, the thermoplastic polymer is a crystallizable polypropylene such as a propylene homopolymer, a random copolymer, or a so-called heterophasic or impact copolymer of propylene and ethylene and / or other alpha-olefins.

According to a preferred embodiment of the present invention, the thermoplastic polymer is a heteropolypropylene copolymer. Such a copolymer basically has at least two phase structure consisting essentially of a propylene based semi-crystalline matrix and a dispersed elastomer phase, generally an ethylene-propylene rubber (EPR). These polypropylenes generally polymerize propylene in the presence of a catalyst system in one or more reactors; Followed by polymerization of the propylene-ethylene mixture; Or may be prepared by blending other (co) polymers. The resulting polymeric material is heterophasic; Studies have shown that four phases, namely, crystalline polypropylene, amorphous polypropylene, crystalline ethylene-propylene rubber, and amorphous ethylene-propylene rubber are present in the heterophasic propylene-based copolymer. The advantage of such polymers is their improved impact resistance, especially at low temperatures.

The thermoplastic polymer is preferably a heterophasic propylene copolymer containing a matrix phase containing propylene and a dispersed phase containing an ethylene-alpha-olefin elastomer.

Preferably, the heterophasic propylene copolymer is a matrix phase comprising a propylene homopolymer and / or a propylene copolymer containing not less than 90 wt% propylene and not more than 10 wt% ethylene and / or one or more C ₄ to C ₁₀ alpha-olefins Alpha-olefin elastomer containing from 60 to 92 wt% of ethylene, from 40 to 65 wt% of ethylene and from 35 to 60 wt% of one or more C ₃ to C ₁₀ alpha-olefins, preferably propylene, . The percentages of the matrix and dispersed components are based on the total weight of the heterophasic propylene copolymer; The comonomer content is based on the copolymer component.

Preferably, the matrix phase is a propylene homopolymer and the mass dispersed phase is an ethylene-alpha-olefin elastomer containing 40-65 wt% ethylene and 35-60 wt% propylene.

The thermoplastic polymer composition according to the present invention preferably contains 0.0025 to 0.1 wt% of the first nucleating agent based on the total thermoplastic polymer composition. The first nucleating agent requires a specific minimum amount to have an effective effect on the nucleation reaction and properties of the polymer composition containing talc as an additional nucleating agent; Accordingly, the nucleating composition preferably contains at least 0.004, 0.005, 0.008, 0.01 wt% of the first nucleating agent. Further, when the amount of the first nucleating agent in the composition is increased to 0.1 wt% or more, it is hardly helpful to improve the properties of the final product. Therefore, it is preferable that the nucleating composition contains 0.08, 0.06, 0.05, 0.03 wt% or less of the first nucleating agent. Thus, a particular advantage of the present invention is that relatively small amounts of the first nucleating agent can be applied with the talc-based second nucleating agent; It not only improves performance, but also provides cost savings.

The amount of talc used as the second nucleating agent in the polymer composition is preferably 0.1 to 5 wt%, more preferably 0.2 to 4 wt%, based on the total thermoplastic polymer composition; Or 0.3 to 3 wt%. Talc needs a certain minimum amount to provide nucleation effect and good mechanical properties, such as stiffness. Accordingly, it is preferred that the nucleating composition contain at least 0.2, 0.3 or especially 0.5 wt% of talc. If the nucleating composition contains more than 5 wt% talc, this additional amount will act only as a filler. Thus, it is preferred that the nucleating composition contain up to 4 or 3 wt% of talc.

The heterogeneous propylene copolymer of the thermoplastic polymer composition according to the present invention preferably has an MFI of less than 1 dg / min when measured according to ISO 1133 under 230 DEG C and 2.16 kg. The MFI of the heterophasic propylene copolymer may be, for example, 0.1 to 0.5 dg / min.

It is preferred that the thermoplastic polymer composition according to the invention contains no or substantially no organic peroxide. The expression " substantially free of organic peroxide "may mean less than 0.01 wt% of the total composition.

Compositions according to the invention containing this type of propylene copolymer with a low MFI are particularly useful in pipes, in particular sewer pipes and sewer pipes. This field of application is generally characterized by good impact resistance at a handling temperature (carried out according to EN 1852 and EN 13476), high ring stiffness for good dimensional stability (especially important for the outer layer of the pipe), good processability, good chemical resistance, Thermal oxidation resistance, good shrinkage and / or low specific gravity. Plastic pipe producers are making great efforts to increase their market share from conventional materials (ie clay, concrete and cast iron) in the sewer pipe market. Typical applications are corrugated pipes and solid waste water pipes. Accordingly, the present invention relates to a pipe containing a thermoplastic polymer composition according to the present invention containing such a propylene copolymer.

Preferably, the propylene homopolymer on the matrix has an MFI of less than 1 dg / min, such as 0.1 to 0.5 dg / min.

Preferably, the dispersed phase ethylene-alpha olefin elastomer has an MFI of 0.001 to 0.1 dg / min.

The thermoplastic polymer composition according to the present invention preferably has a density in the range of 890 to 920, such as 900 to 910 kg / m3, for example, a density of about 905 kg / m3.

The thermoplastic polymer composition according to the present invention has good thermal oxidation resistance, for example, the oxidation resistance (OIT) is at least 100 min as measured according to EN 728: 1997.

The thermoplastic polymer composition according to the present invention has EN 1852 (20 & 110 mm) at 80 DEG C (e.g. at least 140 hours at 4.2 MPa, preferably at least 1000 hours at 4.2 MPa) Pipe), it is desirable to have good pressure resistance.

The thermoplastic polymer composition according to the present invention is similar in MFI to the MFI of the difunctional propylene copolymer in this thermoplastic polymer composition. The MFI of the thermoplastic polymer composition according to the present invention may be less than 1 dg / min, such as 0.1 to 0.5 dg / min.

The thermoplastic polymer composition according to the present invention has a high stiffness. For the present invention, the stiffness is measured by measuring the flexural modulus according to ASTM D790-10. The flexural modulus was measured in parallel (flexural modulus II) and vertical (flexural modulus L) orientations according to ISO 37/2 for 3.2 mm thick specimens.

The thermoplastic polymer composition according to the present invention preferably has a flexural modulus L of at least 1500 MPa, preferably at least 1600 MPa, more preferably at least 1700 MPa, more preferably at least 1800 MPa, such as at least 1850 MPa.

The thermoplastic polymer composition according to the present invention preferably has a flexural modulus II of at least 1500 MPa, preferably at least 1600 MPa, more preferably at least 1700 MPa, more preferably at least 1800 MPa.

The thermoplastic polymer composition according to the present invention possesses a sufficient degree of impact strength. For the present invention, the impact strength is measured by measuring the Izod impact strength at 23 ° C in accordance with ISO 180 4A: Test geometry: 65 * 12.7 * 3.2 mm, ISO 37/2 parallel (impact strength II) Notch 45 ° according to impact strength L).

The thermoplastic polymer composition according to the present invention preferably has Izod impact strength L (23 캜, kJ / m 2) of at least 10, preferably at least 12, more preferably at least 16.

The thermoplastic polymer composition according to the present invention preferably has Izod impact strength II (23 캜, kJ / m 2) of at least 3, preferably at least 4, more preferably at least 4.5.

The thermoplastic polymer composition according to the present invention has a Charpy notch impact strength of at least 50 kJ / m 2, such as about 60 kJ / m 2 when measured at 23 ° C using ISO 179-1: 2010, The Charpy Notch impact strength of the thermoplastic polymer composition is at least 25 kJ / m 2, such as about 35 kJ / m 2 (measured using ISO 179-1: 2010 at 0 캜) as measured at 0 캜. The thermoplastic polymer composition Is preferably at least 5 kJ / m 2, for example, about 6 kJ / m 2 when measured at -20 캜 using ISO179-1: 2010.

The present invention also relates to an article, preferably a pipe containing the thermoplastic polymer composition of the invention, the thermal oxidation resistance of which is at least 100 min as determined using EN 728: 1997, The pressure resistance of the article shall be at least 1000 hours at 4.2 MPa when measured at 80 ° C in accordance with EN 1852 (20 & 110 mm pipe). The pressure resistance of this article shall be 95 ° C according to EN 1852 (20 & (Or at least 3000 hours at 2.5 MPa)

The Charpy Notch impact strength of the thermoplastic polymer composition is at least 50 kJ / m 2, such as about 60 kJ / m 2, as measured at 23 ° C using ISO 179-1: 2010,

The Charpy Notch impact strength of the thermoplastic polymer composition is at least 25 kJ / m 2, such as about 35 kJ / m 2, as measured at 0 캜 using ISO 179-1: 2010,

The Charpy Notch impact strength of the thermoplastic polymer composition is at least 5 kJ / m 2, such as about 6 kJ / m 2, as measured at -20 캜 using ISO 179-1: 2010.

The thermoplastic polymer composition according to the present invention may contain other additives, and suitable examples thereof include a clarifier, a stabilizer such as a UV stabilizer, an acid scavenger, a release agent, a plasticizer, an antioxidant, a lubricant, an antistatic agent, Anti-fogging additives, slip additives, antiblocking additives, polymer processing aids, organic peroxides to control melt rheology, and the like, as well as additives such as antioxidants, antioxidants, antioxidants, . Such additives are well known in the art. Those skilled in the art will know how to use these additives in their usual effective amounts.

The thermoplastic polymer composition according to the present invention may also comprise one or more conventional additives such as those mentioned above, such as stabilizers such as heat stabilizers, antioxidants, UV stabilizers; Colorants such as pigments and dyes; Refining agents; Surface tension modifiers; slush; Flame retardant; Mold - Release Agent; Flow improvers; Plasticizers; An antistatic agent; Impact modifiers; A blowing agent; Fillers and reinforcing agents; And / or a component that enhances interfacial bonding between the polymer and the filler, such as maleic acid chlorinated polypropylene, wherein the thermoplastic polymer is a polypropylene composition. One skilled in the art can readily select any suitable combination of additives and the amount of additive without undue experimentation. The amount of additive depends on its type and function; Generally 0 to about 30 wt%, based on total composition; Preferably 0 to about 20 wt%; More preferably 0 to about 10 wt%; Most preferably from 0 to about 5 wt%.

The thermoplastic polymer composition of the present invention can be obtained by mixing the nucleating composition according to the present invention with a thermoplastic polymer, and optionally other additives, using any suitable means. The thermoplastic polymer composition of the present invention is preferably produced in a form that permits easy processing into molded articles in subsequent steps, such as pellets or granules. The composition may be a mixture of various particles or pellets; Such as a blend of a thermoplastic polymer and a masterbatch of a nucleating composition or a blend of pellets of a thermoplastic polymer containing one of the two nucleating agents and fine particles containing pellets of another thermoplastic polymer, Blend < / RTI > The thermoplastic polymer composition of the present invention is preferably in the form of pellets or granules obtained by mixing all components in an apparatus such as an extruder; The advantage is that the composition has a uniform and well defined concentration of nucleating agent (and other components).

The thermoplastic polymer composition can then be processed into shaped articles by any conventional technique known in the art. Suitable examples include injection molding, injection blow molding, injection stretch blow molding, rotary molding, compression molding, extrusion and extrusion compression molding, extrusion blow molding, sheet extrusion, film extrusion, cast film extrusion, Thermoforming.

Accordingly, the present invention also relates to a molded article containing the thermoplastic polymer composition according to the invention. Examples of shaped articles include injection molded articles, extruded films, profiles or pipes, and thermoformed cups.

Particularly suitable articles are pipes, especially sewage and waste water pipes. Accordingly, the present invention relates to a pipe containing the thermoplastic polymer composition according to the invention.

While the invention has been described in detail for purposes of illustration, it is to be understood that such detail is solely for that purpose and that those skilled in the art will be able to make variations without departing from the spirit and scope of the invention as defined in the claims.

Moreover, in particular, the present invention relates to all possible combinations of features described herein, and particularly preferably to combinations of features set forth in the claims.

It is also to be noted that the term "containing" does not exclude the presence of other elements. However, it should be understood that the description of the products containing the specific ingredients may also disclose the products comprising these components. Likewise, it should be understood that the description of how to include specific steps may also disclose a method comprising these steps.

As used herein, the range of "A to B" values should be understood to mean "at least A to maximum B ".

The present invention will now be described, but not limited to, the following embodiments.

Example

Example 1

Several samples were prepared using starting materials with a melt flow rate (MFI) of 0.32 dg / min. This material contains a propylene polymer matrix in which the propylene-based matrix (propylene homopolymer in this case) is present in an amount of 91 wt% based on the total heterogeneous propylene copolymer, and 9 wt% of an ethylene-propylene copolymer consisting of 58 wt% ethylene Propylene homopolymer.

The heterophasic propylene copolymer (3.75 kg) was extruded in a twin screw ZE21 extruder with 2.5 wt% decalcom (Imerys steamic OOSD / G microdialcum). The formulation of this material additionally contained 500 ppm of processing aid calcium stearate, 500 ppm of processing aid zinc stearate, 4000 ppm of stabilizer Irganox 1010, 1500 ppm of stabilizer Irgafos 168 and 250 ppm of HPN20E. The additives, talc and nucleating agent were mixed with the heterophasic copolymer and then put into the hopper of the extruder.

The temperature profile of the extruder was 20-20-30-50-100-170-220-220-240 DEG C at a throughput of 2.5 kg / h under 300 rpm.

For the present invention, the stiffness was measured by measuring the flexural modulus according to ASTM D790-10. The flexural modulus was measured for 3.2 mm thick specimens according to ISO37 / 2, parallel and vertical orientation.

For the present invention, the impact strength is measured by measuring Izod impact strength at 23 DEG C in accordance with ISO 180 4A. Test geometry: 65 * 12.7 * 3.2 mm, ISO 37/2 Notch, 45 °.

For the purposes of the present invention, the flow is measured by measuring the so-called melt flow index or the melt flow rate, referred to as the melt index, according to ISO 1133 (2.16 kg / 230 ° C).

For the purposes of the present invention, CLTE is measured in accordance with ASTM D696 in parallel and perpendicular directions. Two types of temperature changes are used for the measurement: a temperature change of 20 ° C to 80 ° C and a temperature change of -30 ° C to 30 ° C.

For the purposes of the present invention, the shrinkage factor 3-D is measured according to ISO 294-4. Two types of shrinkage were measured: shrinkage after 24 hours at 23 ° C and shrinkage after 24 hours at 23 ° C and then after 1 hour at 90 ° C.

The results are summarized in Tables 1 and 2. In the table,

RC is the rubber content (propylene-ethylene copolymer) present in the heterophasic copolymer; RCC2 is the C2 (ethylene) content present in the rubber portion of the polymer.

RC and RCC2 were measured by IR spectroscopy and were calibrated using NMR according to known procedures.

The MFI diisocyanate copolymer is the MFI of the starting diisocyanate copolymer consisting of matrix and rubber.

The MFI final is the MFI of the final extruded composition of the additive, such as the heterophasic copolymer and talc, the nucleating composition and the peroxide.

Properties in the parallel and vertical directions are indicated by "II" and "L", respectively.

Comparative experiment

A comparative experiment was carried out and the properties were measured as summarized in Tables 1 and 2.

CEx1 CEx2 CEx3 Ex1 CEx4 CEx5 Matrix (wt% based on heterogeneous copolymer) 91.0 91.0 91.0 91.0 91.0 91.0 RC (wt% based on heterogeneous copolymer) 9.0 9.0 9.0 9.0 9.0 9.0 RCC2 (wt%) 58 58 58 58 58 58 MFI matrix (dg / min) 0.44 0.44 0.44 0.44 0.44 0.44 MFI rubber (dg / min) 0.006 0.006 0.006 0.006 0.006 0.006 MFI diisocyanate copolymer (dg / min) 0.32 0.32 0.32 0.32 0.32 0.32 Talc (wt%) 0 2.5 0 2.5 0 2.5 HPN20 (wt%) 0 0 0.05 0.05 0 0 ADK NA27 (wt%) 0 0 0 0 0.1 0.1 Additive (wt%, stabilizer Irganox 1010) 0.4 0.4 0.4 0.4 0.4 0.4 Stabilizer Irgafos 168 (wt%) 0.15 0.15 0.15 0.15 0.15 0.15 Calcium (wt%) acid scavenger stearate 0.05 0.05 0.05 0.05 0.05 0.05 Acid scavenger zinc stearate (wt%) 0.05 0.05 0.05 0.05 0.05 0.05 Bending modulus of elasticity L (MPa) 1504 1805 1755 1854 1591 1694 Bending modulus of elasticity II (MPa) 1542 1813 1740 1849 1823 1916 Izod impact L (23 캜, kJ / m 2) 12.43 14.8 19.8 18.0 16.4 17.8 Izod impact II (-20 ° C, kJ / ㎡) 4.6 4.8 5.2 4.7 5.11 4.77

A comparison of CEx2, CEx3 and Ex1 shows that the combination of talc and HPN20 shows a synergistic effect on the flexural modulus. Also, the impact strength is increased.

A comparison of CEx1 and CEx4 shows that ADK NA27 also increases the flexural modulus but the increase in flexural modulus L is very small.

Also, the comparison of CEx1, Ex1 and CEx5 shows that the combination of talc and HPN20 results in a large increase in flexural modulus L and II, whereas the combination of talc and ADK NA27 results in only a large increase in flexural modulus II and the flexural modulus L increases .

CEx6 CEx7 CEx8 CEx9 Ex2 CEx10 Ex3 Matrix (wt% based on heterogeneous copolymer) 91.0 91.0 91.0 91.0 91.0 91.0 91.0 RC (wt% based on heterogeneous copolymer) 9.0 9.0 9.0 9.0 9.0 9.0 9.0 RCC2 (wt%) 58 58 58 58 58 58 58 MFI matrix (dg / min) 0.44 0.44 0.44 0.44 0.44 0.44 0.44 MFI rubber (dg / min) 0.006 0.006 0.006 0.006 0.006 0.006 0.006 MFI diisocyanate copolymer (dg / min) 0.36 0.36 0.38 0.37 0.40 0.36 0.39 Talc (wt%) 0 0.5 0 0 0.5 0.5 5 HPN20E (wt%) 0 0 0.025 0 0.025 0 0.025 HPL68L (wt%) 0 0 0 0.05 0 0.05 0 Additive (wt%, stabilizer Irganox 1010) 0.4 0.4 0.4 0.4 0.4 0.4 0.4 Stabilizer Irgafos 168 (wt%) 0.15 0.15 0.15 0.15 0.15 0.15 0.15 Calcium (wt%) acid scavenger stearate 0.05 0.05 0.05 0.05 0.05 0.05 0.05 Acid scavenger zinc stearate (wt%) 0.05 0.05 0.05 0.05 0.05 0.05 0.05 Bending elastic modulus L (23 DEG C, MPa) 1604 1696 1775 1625 1844 1747 1975 Bending modulus of elasticity II (23 DEG C, MPa) 1666 1715 1752 1769 1826 1864 2001 Izod impact L (23 캜, kJ / m 2) 12.36 12.08 15.63 11.03 14.65 9.91 15.09 CLTE 20 占 폚 -80 占 폚 (占 퐉 / mK) 140.0 128.4 115.4 152.8 114.9 150.5 114.41 CLTE -30 占 폚 -30 占 폚 (占 퐉 / mK) 101.7 90.7 77.8 112.3 76.8 112.1 73.529 Shrinkage L (%) after 24 hours at 23 ° C 2.0898 1.9106 1.4405 1.9293 1.4352 1.9079 1.4434 Shrinkage L (%) after 24 hours at 23 DEG C + 1 hour at 90 DEG C 2.0976 1.9470 1.5816 2.2071 1.5867 2.1817 1.5866

A comparison of CEx 7, CEx 8 and Ex 2 shows that the combination of talc and HPN20 has a synergistic effect on flexural modulus.

Comparison of Ex 2 with CEx 10 shows that the combination of talc and HPN20 is better in terms of impact strength, CLTE and shrinkage than the combination of talc and HPN68. In addition, the combination of talc and HPN20 resulted in similar flexural moduli L and II, while the combination of talc and HPN68 resulted in a large difference between the flexural moduli L and II. Large differences between the flexural moduli L and II lead to undesirable large internal stresses.

Also, a comparison of CEx 6, Ex 2 and CEx 10 shows that the combination of talc and HPN20 greatly improves impact strength, CLTE and shrinkage as well as flexural modulus, while the combination of talc and HPN 68 worsens CLTE and shrinkage .

Claims (15)

(a) a first nucleating agent containing a cyclic dicarboxylate salt compound; And
(b) a nucleating agent comprising a second nucleating agent containing talc, wherein the cyclic dicarboxylate salt compound is represented by formula (I):
(I)

The nucleating composition of claim 1, wherein the weight ratio of the first nucleating agent to the second nucleating agent is from 1: 1200 to 2: 1, preferably from 1:50 to 1: 5. 10. A thermoplastic polymer composition containing the nucleating composition according to any one of claims 1 to 9 and a thermoplastic polymer. The thermoplastic polymer composition according to claim 3, wherein the amount of the first nucleating agent is 0.0025 to 0.1 wt%. The thermoplastic polymer composition according to claim 3 or 4, wherein the amount of the second nucleating agent is 5 wt% or less, preferably 0.1 to 3 wt%. 6. A process according to any one of claims 3 to 5, wherein the thermoplastic polymer is a matrix phase comprising propylene and a heterophasic propylene copolymer containing a dispersed phase containing an ethylene-alpha-olefin elastomer Chain thermoplastic polymer composition. 7. The composition of claim 6, wherein the heterophasic propylene copolymer contains from 60 to 92 wt% of the matrix phase and from 8 to 40 wt% of the dispersed phase, wherein the matrix phase comprises propylene homopolymer and / or at least 90 wt% propylene and up to 10 wt% of ethylene and / or at least one C ₄ to C ₁₀ alpha-and containing a propylene copolymer containing an olefin, the ethylene on the dispersion-alpha-olefin elastomer is from 40 to 65wt% of ethylene and 35 to the 60wt%, at least A thermoplastic polymer composition containing one C ₃ to C ₁₀ alpha-olefin, preferably propylene. The thermoplastic polymer composition according to claim 6 or 7, wherein the propylene homopolymer has an MFI of less than 1 dg / min. The thermoplastic polymer composition of claim 8, wherein the matrix phase has an MFI of less than 1 dg / min. The thermoplastic polymer composition according to claim 8 or 9, wherein the dispersed phase ethylene-alpha-olefin elastomer has an MFI of from 0.001 to 0.1 dg / min. 11. The thermoplastic polymer composition according to any one of claims 8 to 10, wherein the MFI is 0.1 to 0.5 dg / min. The method according to any one of claims 8 to 11, wherein the flexural modulus L is 1,500 MPa or more, preferably 1,600 MPa or more, more preferably 1,700 MPa or more, more preferably 1,500 MPa or more, Is at least 1800 MPa. The thermoplastic polymer composition according to any one of claims 8 to 12, wherein the Izod impact strength L (23 캜, kJ / m 2) is 10 or more, preferably 12 or more, more preferably 16. A molded article comprising the thermoplastic polymer composition according to any one of claims 3 to 13, wherein the thermo-oxidative resistance of the article is at least 100 min as measured according to EN 728: 1997, , The pressure resistance of this article is measured at 80 ° C in accordance with EN 1852 (20 & 110 mm pipe), it is more than 1000 hours at 4.2 MPa, or the pressure resistance of this article is 95 (Or at least 2.5 kPa) of at least 50 kJ / m < 2 >, such as at least about 60 kJ / cm2 measured at 23 DEG C according to ISO 179-1: / M < 2 >, for example at least 25 kJ / m 2, such as about 35 kJ / m 2 as measured at 0 ° C according to ISO 179-1: 2010 (or alternatively the thermoplastic polymer composition Charpy Notch Impact Strength of ISO 179- 1: 2010, at least about 5 kJ / m < 2 >, for example about -20 < 0 > C, measured at -20 deg. 15. The shaped article of claim 14, wherein the article is a pipe.